O-alkyl-(thiono) thiol-s-(s-alkylmercapto-s-benzylmercapto-methyl)-phosphoric (phosphonic) acid esters

ABSTRACT

IN WHICH R1 is alkyl or alkoxy of 1 to 6 carbon atoms, R2 is alkyl of 1 to 6 carbon atoms, R3 is alkyl of 1 to 6 carbon atoms, X is oxygen or sulfur, Y is chlorine, and N IS 0, 1 OR 2, WHICH POSSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.   O-alkyl-(thiono)thiol-S-(S&#39;&#39;-alkylmercapto-S&#39;&#39;&#39;&#39;-benzylmercaptomethyl) -phosphoric (phosphonic) acid esters of the formula

United States Patent [1 1 Schrader et al.

[54] O-ALKYL-(THIONO) THlOL-S-(S-ALKYLMERCAPTO-S- BENZYLMERCAPTO-METHYL)- PHOSPHORIC (PHOSPHONIC) ACID ESTERS [75] Inventors: Gerhard Schrader, Wuppertal;

Ingeborg Hammann, Cologne, both of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany 221 Filed: Feb. 27, 1973 211 App]. No.: 336,316

[30] Foreign Application Priority Data Mar. 7, 1972 Germany 2210836 [52] US. Cl. 260/948, 424/216 [51] Int. Cl A0ln 9/36, C07f 9/16, C07f 9/40 [58] Field of Search 260/948 [56] References Cited UNITED STATES PATENTS 2,959,516 11/1960 Sallmann 260/948 X 3,105,003 9/1963 Walsh et al. 7. 260/948 X FOREIGN PATENTS OR APPLICATIONS 244,258 4/1963 Australia 260/948 [4 Jan. 21,1975

Primary ExaminerLorraine A. Weinbcrger Assistant ExaminerRichard L. Raymond Attorney, Agent, or FirmBurgess, Dinklagc & Sprung [57] ABSTRACT O-alkyl-(thiono)thiol-S-[S-alkylmercapto-S"- benzylmercapto-methyl]-phosphoric acid esters of the formula X R SR P--S O'H\ (I) in which 7 Claims, N0 Drawings (phosphonic) O-ALKYL-(THIGNO) THlOL-S-(S-ALKYLMERCAPTO-S- BENZYLMERCAPTO-METHYL)-PHOSPHORIC (PHOSPHONIC) ACID ESTERS 5 X is oxygen or sulfur,

The present invention relates to and has for its ob- Y is Chlorine, and jects the provision of particular new O-alkyl-(thiono) n is 1 or 2, th 'alkylmggap -Sfgbw y mergap o-m t l- Preferably, R is optionally halogen-substituted lower p ph (p p n acid esters optionally chloalkyl or alkoxy with 1 to 4 carbon atoms such as rine substituted on the benzene ring, which possess i l0 methyl, methoxy, ethyl, ethoxy, B-chloroethoxy, secticidal and acaricidal properties, active composi- [3- h] h flfifiq i hl rh or i m l, tions in the form of mixtures of such compounds with nor iso-propoxy, 1-, iso- 0r 5ec -butyl 0r is( or solid and liquid dispersible carrier vehicles, and methsec.-butoxy, R is optionally halogen-substituted lower ods for producing such compounds and for using such alkyl with l 4 carbon atoms such as methyl, ethyl, compounds in a new way especially for combating ,B-chloroethyl,B,B,B-trichloroethyl, nor isopropyl, n-, pests, e.g., insects and acarids, with other and further isoor sec.-butyl, R, and R possibly being the same or objects becoming apparent from a study of the within different from each other, R is methyl or ethyl, and n specification and accompanying examples. iS

In German Patent Specifications Nos. 830,509 and The inventicrl also PKWides a Process for the P 947,369 th are d ib d (),()-di h l s tion of such a compound in which a thiolor thionothil t h l]- hi lor hi hi L ol-phosphoric (-phosphonic) acid salt of the general phosphoric acid esters, for example 0,0-diethyl-S-[(4- formula methylphenylmercapto)-methyl]-thiol-(Compound A) and 0,0-diethyl-S-[phenylmercaptomethyl]-thionothiol-phosphoric acid ester (Compound B). The informa- R X tion given in these specifications indicates that these 1 products are distinguished by an outstanding insecticidal effectiveness. R 0 (11) Furthermore, from German Published Specification DAS No. 1,148,549 the analogous thionothiolphosphomc acld esters fol.- exaniple ethyI'O'FthyI'S' is reacted with a benzylmercapto-monohalomethyl [phenylmercaptomethyl]-thionothiolphosphomc acid alkyl thioether Ofthe enera] formula ester (Compound C) and the corresponding 2-, 3- and g 4-chlorophenylmercapto derivatives, are also known. These compounds likewise possess insecticidal propers ties.

The present invention provides thiolor thionothiol- Hal-CH S-[S-alkylmercapto-S"-benzylmercapto-methyl]- S-CH -Q phosphoric or -phosphonic acid esters of the general 40 (III) formula in which X SR R R R X, Y and n have the same meanings as. 1 3 above, M is a univalent metal equivalent or ammo- P-S-CH nium, and Hal is chlorine or bromine. R The course of the process can be represented by the 2 2 (I) following reaction scheme (IV) X R SR P-S-M Hal-CK 5 (Y) Hal m 32 zg (II) (III) X R S 1\ P-S-C R3 (IV) n R 0 s-ca -g in which R, is alkyl or alkoxy of l to 6 carbon atoms, R is alkyl of l to 6 carbon atoms, R is alkyl of l to 6 carbon atoms,

M stands preferably for an alkali metal ion, particularly potassium or sodium, or ammonium.

The benzylmercapto-monohalomethyl alkyl thioethers of the general formula (III) required as starting materials are readily available even on an industrial scale, for example by the following route:

Benzylmercaptan is reacted with monochloromethyl ethyl thioether according to the following equation (a) to give benzylmercaptomethyl ethyl thioether and the The process according to the invention for the preparation of the compounds of formula (I) is preferably carried out in the presence of a solvent or diluent. As

such, practically all organic solvents inert to the reactants are suitable. These include hydrocarbons which may be chlorinated, such as benzene, toluene, xylene and chlorobenzene; and ethers, for example diethyl and dibutyl ether and dioxane. For this purpose, however, low-boiling aliphatic ketones or nitriles such as acetone, methyl ethyl, methyl isobutyl and methyl isopropyl ketone, acetonitrile and propionitrile, have proved particularly satisfactory.

The reaction may be carried out within a fairly wide temperature range. In general, the reaction is carried out at about to 80C or the boiling point of the reaction mixture if lower than 80C, preferably at to 70C.

According to the equation (IV) recited above, in the reaction equimolar amounts of benzylmercaptomonohalomethyl alkyl thioether and of thiolor thionothiol-phosphorie(-phosphonic) acid salt are theoretically necessary.

Expediently, a mixture of (thiono)thiol-phosphoric(- onic) acid salt and one of the above-mentioned solvents, preferably acetonitrile, is provided, and the benzylmercapto-halomethyl ethyl thioether is added dropwise to this mixture. After completion of the addition, the reaction mixture is, in order to complete the reaction, stirred for a further 1 to 3 hours, possibly with slight heating, and it is then cooled to room temperature. The working up of the mixture may take place in customary manner by taking up the separated reaction product in most cases as an oil, in one of the hydrocarbons mentioned above, preferably benzene, washing and drying the organic phase and evaporating the solvent.

The new compounds are obtained in most cases in the form of colorless to slightly yellow-colored, waterinsoluble oils which cannot, even under greatly reduced pressure, be distilled without decomposition. They can be characterized by their refractive indices.

The thiolor thionothiol-phosphoric or -phosphonic acid esters according to the invention are distinguished by outstanding insecticidal, acaricidal and, in many cases, fungitoxic and rodenticidal properties, with, in some cases, extremely low phytotoxicity. The products may therefore be used in crop protection and the protection of stored products, as well as in the hygiene field, for the control of noxious sucking and biting insects, Diptera and mites (Acari).

To the sucking insects there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the current gall aphid (Crypmmyzus korschelti), the rosy apple aphid (Sappaphis muli), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseuducoccus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus inter medias), the bed bug (Cimex Iectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triumma infestans) and, further, cicadas, such as Euscelis bilohatus and Nephotettix bipunctatus.

In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipenm's), the gypsy moth (Lymantria dispar), the browntail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segemm), the large white butterfly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda) and cottom worm (Prodem'a litura), the ermine moth (Hyponomeula padella), the Mediterranean flour moth (Ephesn'a kuhniellu) and greater wax moth (Galleria mellonella).

Also to be classed with the biting insects are beetles (Coleoptera), for example the granary weevil (Simphilus granarius Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (lhaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomenmsus), the bean weevil (Bruchidius Acanthoscelides obleclus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granarium), the flour beetle ('l'riholium castaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Sleguhium paniceum), the yellow mealworm (Tenebrio molilor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the eockchafer (Melolontha melolonlha); cockroaches, such as the German cockroach (Blaltella germanica), American cockroach (Periplanela americana), Madeira cockroach (Leucophaea or Rhyparobia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Gryllus domesticus); termites such as the eastern subterranean termite (Reticulitermesflavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger).

The Diptera comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia cam'cylaris), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acari) there are classed, in particular, the spider mites (Tetranychidae) such as the twospotted spider mite (Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonychus ulmi), gall mites, for example the black current gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus lalus) and the cyclamen mite (Tarsanemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata).

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the novel products are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e., plant compatible or herbicidally inert) pesticide diluents or extenders, i.e., diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g., conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon, inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g., chlorobenzenes, etc.), cycloalkanes (e.g., cyclohexane, etc.), paraffins (e.g., petroleum or mineral oil fractions), chlorinated aliphatic hydrocar bons (e.g., methylene chloride, chloroethylenes, etc.), alcohols (e.g., methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g., glycol monomethyl ether, etc.), amines (e.g., ethanolamine, etc.), amides (e.g., dimethyl formamide, etc.),

sulfoxides (e.g., dimethyl sulfoxide etc.), acetonitrile, ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g., kaolins, clays, alumina, silica, chalk, i.e., calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g., highly dispersed silicic acid, silicates, e.g., alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g., surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g., polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearatc, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one a'nother and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides and acaricides or rodenticides, fungicides, bactericides, nematocides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95 percent by weight, and preferably 0.5- percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10 percent, preferably 0.01-1 percent, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g., a surface-active agent, such as an emulsifying agent and- /or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001- percent, and preferably 0.01-95 percent, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e., by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g., average particle diameter of from 50100 microns, or even less, i.e., mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1,000 g/hectare, preferably 40 to 600 g/hectarc, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95 percent by weight of the active compound or even the 100 percent active substance alone, e.g., about 20-100 percent by weight of the active compound.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

Furthermore, the present invention contemplates 5 EXAMPLE 1 methods of selectively killing, combating or controlling Phaedon larvae test pests, e.g., insects and acarids, which comprises apply- Solvent: 3 parts by weight acaone ing to at least one of correspondingly (a) such insects, Emulsifierz 1 part by weight alkylarylpolyglycol ether (b) such acarids, and (f) the corresponding habitat To produce a Suitable preparation of active thereof, i.e., the locus to be protected, a correspondpound, 1 part by weight of the active Compound was ihgly combative or toxic amount an msecncldany mixed with the stated amount of solvent containing the or acaricidally effective amount, of the particular ac- Stated amount f emulsifier, and thg concentrate was live compound of the invention alone or together with diluted with water to the desired concentration. a carrier vehicle as noted above. The instant formula- Cabbage haves (Bmssica Olemcea) were Sprayed lions or composltlohs are p in the h h manner with the preparation of the active compound until dripfor instance y Spraylhg, atomlzlhg, Vaponzmgv Scatter ping wet and then infested with mustard beetle larvae ing, dusting, watering, squirting, sprinkling, pouring, (phaedon cochleariae), fumigating, dressing, encrustation, and the like. After the specified periods of time, the degree of de- It will be realized, of course, that the concentration struction was determined as a percentage: 100 percent of the particular active compound utilized in admixture means that all the beetle larvae were killed. 0 percent with the carrier vehicle will depend upon the intended means that none of the beetle larvae were killed. application. Therefore, in special cases it is possible to The active compounds, the concentration of the acgo above or below the aforementioned concentration tive compounds, the times of evaluation and the results ranges. can be seen from the following Table 1.

Table l (Phaedon larvae test) Active compound. Concentration Degree of of active destruction compound in 74: in 73 after by weight 3 days s c H 0 2 5 i -s cH -s- (B) 0.1 100 0 11 0 0.01 0

(known) 2 5 i -s-cH -s- -ca (A) 100 C H O 2 5 0.01 o

(Imovm) c H E so a 2 0 01 0 c H 0 s-cn 1 0 0 5 S /SC2H o 1 100 5 (4) 0 01 100 c H 0 S-CH2- c H 0 sc H 2 5 2 5 (1) 0.1 100 0.01 100 C2H5O S-CH2- 2 5 F 5 S; 133 E' s 2" 0.001

EXAMPLE 2 Plutella test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillars of the diamond-back moth (Plutella maculipennis).

After the specified periods of time, the degree of destruction was determined as a percentage: 100 percent means that all the caterpillars were killed whereas percent means that none of the caterpillars were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 2.

Table 2 (Plurella test) EXAMPLE 3 Doralis test (systemic action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate was diluted with water to the desired concentration.

Bean plants (Vicia faba) which had been heavily infested with the bean aphid (Doralis fabae) were watered with the preparation of the active compound so that the preparation of the active compound penetrated into the soil without wetting the leaves of the bean plants. The active compound was taken up by the bean plants from the soil and so reached the infested leaves.

After the specified periods of time, the degree of destruction was determined as a percentage. 100 percent means that all the aphids were killed; 0 percent means that noneof the aphids were killed.

Active compound Concentration Degree of of active destruction compound in 93 in 73 after by weight 3 days S C H 0.1. 100 2 (C) 0 01 0 C H O (known) S %-s-0H -s- (B) I 0.1 0.01 O 2 5 n 0 C H 0 n 0.1

2 5 H -S-Q-CH A (known) 0 H SC 1-1 O 2 5 2 5 0.1 100 c H o s-cH (4) loo 2 5 2 0.001 5 S C H O SC H 2 5 P-s-cu 2 5 (l) 0.1 0 c H 0 S-CH 0. 01 90 The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3.

Es ates (Doralis test systemic action) Active compound Concentration Degree of of active destruction compound in 7 in 3 after by weight 4 days S C H 2 i' -s-cH -s- O C H O (known) 0 a o s 2 5 "-s-cH -s- O C H 0 2 5 (known) o C H 0 2 5 i -s-cn -s- -cn 0.1 o C H 0 2 5 (known) 0 H SC H 0.1 100 2 5 0.01 100 4) 0.001 90 c 5 0 5 CH Q SC H 2 5 $-C{ 2 5 (l) 0.1 100 0.01 100 C H 0 5 CH 6 C H 0 SC H 5 CH (3) 0.1 100 2 5 Q 0.01 100 EXAMPLE 4 spotted spider mite (Tetranychus urlicae) in all stages Tetranychus test (resistant) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained was diluted with water to the desired concentratron.

Bean plants (Phaseolus vulgaris), which has a height of development.

After the specified periods of time, the effectiveness of the preparation of active compound was determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: I00 percent means that all the spider mites were killed whereas 0 percent means that none of the spider mites were killed.

The active compounds, the concentrations of the ac tive compounds, the evaluation times and the results can be seen from the following Table 4.

Table (Tetranychus test resistant) Active compound Concentration Degree of of active destruction compound in ,1 in 75 after by weight 2 days S C H 2 5\' 2 (C) 0.1 O C H O (known) c H o P-S-CH S (B) 0.1 O C H I 2 (known) 0 C H O p-s-cn -s- -CH 0.1 o C l-I 0 (known) S C H SC H 2 i -s-c 2 5 0.1 98 C l-1 0 S-CH -Q (2) 0 C H SC H 2 i -s-c 2 5 0.1 100 4 c H o s Ca -Q S C H 0 SC H 2 5 2 ,(1) 0.1 90 0 x 0 swa -Q 0 v C H O SC H 2 5 P-SC 2 5 (3) 0.1 95 c 5 0 S-CH -Q I The process of this invention is illustrated by the following preparative examples.

EXAMPLE 5 Preparation of the benzylmercapto-monohalomethyl alkyl thioethers required as starting products were carried out for example in the following way:

40C, with stirring; the reaction mixture was stirred for a further 1 hour and it was poured into 400 ml benzene.

- The benzene solution was subsequently washed with ice water, separated and dried over sodium sulfate. in the ensuing fractional distillation there was obtained 186 g (94 percent of theory) of benzylmercaptomethyl ethyl thioether of the hp. 108C/2 mm Hg and the refractive index n 1.5781 (b) 0.5-molar mixture: 99 g benzylmercaptomethyl ethyl thioethcr were dismonochloromethyl ethyl thioether with the refractive index n 1.5752.

0.3-molar mixture:

63 g sodium 0,0-diethylthionothiolphosphate were dissolved in 300 ml acetonitrile. To thissolution there were added at room temperature, with stirring, 70 g benzylmercapto-monochloromethyl ethyl thioether; the mixture was heated to 60 to 70C for a further hour and the reaction mixture was then taken upin 300 ml benzene. The benzene solution was washed twice with, in each case, 70 ml of water and subsequently dried over sodium sulfate. After evaporation of the solvent 100 g (87 percent of theory) of 0,0-diethyl-S-[S'- ethylmercapto-S '-benzylmercaptomethyl -thionothiolphosphoric acid ester were obtained in the form of a colorless, water-insoluble oil with the refractive index n 1.5810.

Calculated for a molecular weight of 382:

P 8.1 found: 7 7.9 S 33.5 32.9

EXAMPLE 6 c 'o s-cn 2 5 2 (2) P 8.5 found: 8.7 s 35.0 34.9

EXAMPLE 7 P-S-C( S-OH2- (3) 0.18-molar mixture:

36 g ammonium 0,0-diethylthiolphosphate were dissolved in 200 ml acetonitrile. To this solution there were added, with stirring, 42 g benzylmercaptomonochloromethyl ethyl thioether; the reaction mixture was heated to C for a further hour and it was then worked up as in Example 1. 46 g (70 percent of theory) of 0,0-diethyl-S-[S-ethylmercapto-S- benzylmercaptomethyl]-thiolphosphoric acid ester were obtained in the form of a colorless, waterinsoluble oil with the refractive index m, 1.5645. Calculated for a molecular weight of 366:

found EXAMPLE 8 C H S-CH 0.18-molar mixture:

the form of a water-insoluble, pale-yellow oil with the refractive index m, 1.5595. Calculated for a molecular weight of 350:

found P 9.8 8.l s 27.4 27.2

' EXAMPLE 9 c H o s Sc H C1CH2/ s-cn 2 5 0.18-molar mixture:

45 g potassium chloromethyl-O-ethylthionothiolphosphonate were dissolved in 200 ml acetonitrile. To'this solution were added, with stirring, 42 g benzylmercapto-monochloromethyl ethyl thioether; the mixture was heated to 65C for a further hour and it was then worked up as in Example 5. There were so obtained 61 g (88 percent of theory) of chloromethyl-0-ethyl-S-[S'- ethylmercapto-S"-benzylmercapto-methyl]-thionothiolphosphonic acid ester with the refractive index m, 1.6002.

Calculated for a molecular weight of 386.5:

9.8 found 7 It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. A thiolor thionothiol-phosphoric or -phosphonic acid ester of the formula in which 4. The compound according to claim 1 wherein such compound is ethyl-0-ethyl-S-[S-ethylmercapto-S"- benzylmercapto-methyl]-thionothiolphosphonic acid ester of the formula LII 5. The compound according to claim 1 wherein such compound is 0,0-diethyl-S-[S'-ethylmercapto-S"- benzylmercapto-methyl]-thiolphosphoric acid ester of the formula 5 P-S-CH C 1-1 0 S-C'H 6. The compound according to claim 1 wherein such compound is ethyl-O-ethyl-S-[S'-ethylmercapto-S"- benzylmercaptomethyl]-thiolphosphonic acid ester of the formula SC H 7. The compound according to claim 1 wherein such compound is chloromethyl-0-ethyl-S-[S'- ethylmercapto-S"-benzylmercapto-methyll-thionothiolphosphonic acid ester of the formula c 11 o s P SC2H5 ClCH \S-CH 

2. A compound according to claim 1 in which R3 is methyl or ethyl, and n is
 0. 3. The compound according to claim 1 wherein such compound is 0, 0-diethyl-S-(S''-ethylmercapto-S''''-benzylmercaptomethyl) -thionothiolphosphoric acid ester of the formula
 4. The compound according to claim 1 wherein such compound is ethyl-0-ethyl-S-(S''-ethylmercapto-S''''-benzylmercapto-methyl) -thionothiolphosphonic acid ester of the formula
 5. The compound according to claim 1 wherein such compound is 0, 0-diethyl-S-(S''-ethylmercapto-S''''-benzylmercapto-methyl)-thiolphosphoric acid ester of the formula
 6. The compound according to claim 1 wherein such compound is ethyl-0-ethyl-S-(S''-ethylmercapto-S''''-benzylmercaptomethyl)-thiolphosphonic acid ester of the formula
 7. The compound according to claim 1 wherein such compound is chloromethyl-0-ethyl-S-(S''-ethylmercapto-S''''-benzylmercapto-methyl) -thionothiolphosphonic acid ester of the formula 